Synthesis and study of polyhalogen-containing cyclic esters as lubricating oil additives

14

M M (3lrsEir~4)v i'l t,'/

duc,ng the ,~ulidn~ca, lnon polrll ~)I ,~nl I 12A l'ruln - "~ql i,~ - ~,~ C P~dyn|elhacrylalc B doe',, n,~t .~how ,,uch Iemperutur~' depre.s~.~nun propcrlte,, Thercl',~r¢.', a vn:,co,~nty additive nnav he prepar~'d hv ~:opulynnerizal~m ~)I decyl melha,.'nylal~' wnlh I¢lrade~,.'ene, Ih~,., addltlw., ~,., m>l ui"ll~ highly re',;t;,,larlt to Ihermal breakd~,,vul, but al,,,o redu~.'(.,,, ~.'h~ud p,~rrll T'hn,, enablr',, Ihe ~'~=polwr=er nndncated t,._~ be rc'e,L)nnmendc'd a',, an e11'¢.,,.'11,,,,'¢',,n'..,,,.'u',,=lv and ,.'h~ud pOlnl depre',,,,inl~ additivv, h~r petroleum lubrr|.'atnn~ ,~il,, SUMMARY

I. Radncal c(~polymernzalion ol'decvlm~lhacrvlal¢ with lelradec.e.ne wa~ examined. A real copolyrner with allernalnori of nl()nomcr unnl,~ wa.s demon.,,trale.d to be R)rmed. 2. (."opolymer.~ .~ynlhestzed a.~ vi,s~.'u.~liy additives for pelruleum lubrncanls, wert' shown to be h,~hly res,stanl t(~ Ihermal breakdown and reduce the .solndificalnon penni (~1' elk. REFERENCES I A. M. T O R O P T S E V A , K. V. BELOGORODSKAYA and Y. M. BONDARENKO, L,,.~bora

Iornyi prakl~kum po khlmni n lekhnulo~.;nn vv,,~k~m~dckulurnykh sovednrlt,nnn, p. 141'1, Khn mnya, t.~'nnn[~iad, I~'72 2 A. M. ~HI./R, Vy,~q~komolckularnvyt" ,,ny~dnnerlnva. p I ~1, Vv',.',hava ~lll~ol;J, Mo.~'ow, 1'~81

I~Uol C'hrm l.J S S R V . I Plnul.ed m PnlJrid

2b, N . , I, r,r,, 14-IH. IqSh

OllJl ~1H'i/8¢', 1110(JO 4- OO ,, 1¢)14'7PcfRHrlrlon l u u r n a h Lid

SYNIMESIS AND STUDY OF POLYHALOGEN-CONTAINING CYCLIC ESTERS AS LUBRICATING OIL ADDITIVES* M. M. GLJ,";E.INOV, R S. BABAYEV, YII. S. ARLrS'T'AMYAN, T' (.; KYAZ.tMOVA .',nd N (3 AVANE'.SYAN

In,,|,lule hi' ()rga.nochh~rine Synfhes=.% Az~rb S.S R Academy nl Scltmce~, (ReceltJed ~ A'luv 19H'~) 'THE.'. hi~her .,,lress and opera.ung cond,ttons of modern machines, h~s rea.wake, nq~l inler¢,,,t in addillve, s whnch nmpart h,gh anti-.seizure and anti-wear properU¢,s to me dorn lubricants und haJogen,,~, partvcularly chlormt', are known to b¢ Ihe most po pular (.'.omponont,s of antn-~eizur¢ additives. Polyhalogen contaimng cyclic e,,,~ter~ arc. parl=cu.larly well known and the=r e1-1¢cl us known [1. 21 I1~ depend laJgoly on scve, rul parameters wtuch charactcr=ze add=hv¢ molecule.,, * Nei'leldllmJya 26, No. I, 12A- I .I I, 1986.

Synthesis and study oi"polyhaJogen-contairdng cyclic eslers

15

Accordingly the present investigation ~s concerned with the synthesis of polyhaIogen-substiluled cyclic ester and the e,xaminatton of the elTect=veness of additives b'a.scd upon them, in relation In the number type and Ioeutmn of halogen atoms in the addfl=ve molecule. Polyhalogen-contaming bicyehc este.rs o1' halogenated acetic acids were exam ined, the characteri,~tics of the compounds used are given in T'abl¢ I 'The synthe,,,=s of some of these compound.,~ ha,, already been described 1~1 and two new compounds (compounds 4 and O) were synthesized using this method 'This work has provided a complete series ol" compounds which are examined to establish inlerrelationships. Compound 4 (I,4,'~,6,7,7 hexachlorobicyclo[2 2.1]hept-'~ en 2 yl ~1' methyl dtbromacotate) was prepared from 1,2, '~,4,<;,c, hexachlorocyclopenta-1,3-dien¢ (6.825 g; 0.025 mole) and allyl ester o1' dthrornueettc acid (6 4'~ g, () 25 mole) wflh hydroquinone (0.01 g), by heatln~ in a sealed glass ampoule at 150"C I'or 8 hr. Vacuum distillahon of the reaclton product Rave a copper yellow, viscou,~ mtermedtale product. Tats product was punfied using thin layer chromatography (TLC). The structure ol" this compound was inferred I'rom IR ,spectra and confirmed by hydrolysis to the bicychc alcohol [4 I. Frequencies typical of the Iollowlng groups were found m the speclrum of the producl obtained: C = O (in the range of 1720 c m - I ) , C = C (1'~8()--1620 cm'~), C - O - C (1020-1110 cm'~), C - Br (6(H.) cm-~) and C - C I (78() cm "~) Compound 6 (I ,4,5,6-telrachh.~ro-7,7 dimethoxybtcyclol2 2. I] hept-";-en-2 yl methyl dtbromacetate) was synthesized by a similar method. 'The product obtained was purife, d by Ihin layer chromatography (TLC) and the struelure monitored by IR spectroscopy. Frequencies lypical o1" the I'ollowmg groups were found tn the sp¢c trum ot'lhiscompound: C = O(m the range ol" 177()cm- '), C = C(1615 cm), C - O - C (1150, 1205, 1290 c m ' l ) , C - B r (61(),.'m -I) and C - C I (610 cm -j) E'.ach compound ,~hown in "('able I was tested in the lubricant (,-'-22() (GOST 8463-76) in equal molar coneentrutmns (()0746 mole/I ) Tests were earrlt'd out tn a four-hall I'rlcti~n maehtn¢ 'T'R 4 using steel balls (ShKh15) 12.7 mm diameter =n air at I X"-2()"C The rate ol',,lip was () 2 t m/,~ec (6()()rev/mm). Antt-se=z.ure properties of off S-220, ccmtaining a given compound as add=live, were delermmed by gradually stressing the sphere,, AI each slress level, I'rlction was apphed I~.~the '~pheres w~th restored surl'aee,ln the presence ~1" a Fresh batch of lubricant for 0(I set' During testing each eompc~und Ihe .seizure load (Pk) was recorded and the gen eral wear index (GWI) was determined as the average arithmetical ratio ofa~t.al loads relative to the wear or the spheres. The anti wear properties of each lubricant compositions (wear ~nde~, D,,) were determined aecordmg to G(.')S'T' 949(')-7<; under a load of 367.~i N and at a rate of slip of 0.23 m/see Results given ~n Table 2 and compared with similar charactertslacs for od S-220 as control. It follows from 'Table 2 that in those cases when halogen aloms are absent from the additive molecule, the lubricant is not very elTective. Efficiency in-

~ABLE

I

~AIN

C'HARA(.'TIE',RI~Ti(:'!I

(iF l PI|L,~IIHALI(N3BN CI(jr'~I"~.ININ(J

( If'qlLIql EI'jTIEIRq, i)F

AII'EITll( "l ANIt

H h, Llq.t4JE,~q A,("IE I"lq- A4 lit)% ~l'lCld i

(.'ll ~mpl ~und

N~

I

IT

II t,]

I' ....

(

,ll, F

l

lllih

----d

o

111~lll i

(

tPl P,~)

I

,/4

Ill

rvl

'

~i I

H

j

1

m,

l..I 7 %l..I

"

q)l'~

Ihh

4';~I ;, 2,4)

,I C I ~,,,IIII I ~ Ill' I Illl, l~

(

II ,,, !

I I ,, l,( ' ~ IIH 11

II

47

I ~,4- 1%") ( 2(',6 h4 )

',, b.i.(l

'~7'+

q.I ql

q :I /'I l'~ Illlll., ,llll~

ll,q~in I --4lll r' l 9~

41

4L)

I~7

17h~X

iJ~l 17~

Xqql

", 3() hX

'' l ~, ,lLlpllpldlpill'lJl ql

ql

ll'/F'lll "+"-- q II,,q HIi--¢ I ,,,,|

C Ic f

"l

I!EIr;

+1! t-j .

,,,

Xl +2l

1 7h-I 7X (11,1 ~ )

hl 4

I~JX- 190 (I I1 12)

I l '~ 7t~

.+ 0999

h(lq hl,l

lhq-ll71

I 'HI',

1.7,4'~t

'+ZI ~+1

I ,.h~++

I hX(')8

4 I h (19

, ,f"' " ¢1

'l'rl 4111

II ,qbil--i Br, (,

"• ,,

,,,I" Ill

CI CjfJ'~',,,r-~-H,.q.

~

,.,,(. ,4.~H :1}, l

HBr,

71'1,4

11

(lOb 0'~)

ii Cl ;I l

T

~llq

i

llq),I

i

e."l

*

CeJq~uld~d

l~.JalllW mulaJ m,.~,+,l

41

74 h~

I 0'~ l I (Jb

Synlhesis and ,,,ludy of polybalogcn-conta,imn8 cyclic esters

17

T ~ t u r J 2. RJ~qUL.'I'R OF' 'rI~TINO POLYHALOGEN-CON'T'AININO CYCLIC BS'I'BRS OF ACIB'nC AND HALOGENACSt,C ACIT..tS AS LUBRICA'I1NG OIt, (C.2~.0) / ~ D I T W ~ (/tDDITI'VB CUNC]BNTRATION 0"0746 m o l ¢ / I . )

No.

]

I 2 ~1 4

I

Pk, N

D,,,

mm

q'¢~'~ It~l '7

0"¢7 t) '~8

1764 1911

0 bI ()~2

GWI

No

bl 23 t)~.4 7 II12 1222

Pk,

N

D,,,

mm

GW1

'~ t~

'22.0~ It'll

0 ~2 ()'ff2

f2~'47 f 2 I.tY~

'7 8

I (~90 ¢, 882

f)'h4 (1 l-d)

I 0q'4 '~ SHqH

Not~.. Adddtvey I -'7 eurre.'.r,poad h'p Ihe ,JUIJ~.IIJI.IIIotmul~l¢' qtl tl~mr,.HJnd,~ m T.Jble D,, - wear mdt'w,, l..~W'- Kener;JI w~'ar mdex

8 - .il S 220, PE - hp~ld~eitur¢,

creases sharply when chlorme atoms are introduced =nlo the r,=,g of the add=live molecule (compound 2) Apparently, in this situation chlorme-conlam~ng breakdown products of the additive form a protectmg layer on the metal surface which prevent the seizure of sud'aces under friction At the same tmle experience with compounds 4 and 6 indicate that not all chlorine atoms in the rmg take part m this process, smce replacement of chlorme atoms m pos,tron '7,7 for a dimethoxy group has practically no effect upon the frichon characteristics l

1/10

:,?

7

J b'5 q

i, 3

6O

'2(I

217(I Heal

sl.'tblhly o f c y c l c e s l e r s el

4(113

h a l o g e n at'ell,; a t l d s .

t;O0 t , *'C

'The c u r v e n u m b e r s c o r r e s p o n d

Io Ibe

n u m b e r s in T a b l e I.

Data tn "Fable 2 indicate thai the presence of chlorme atoms in Ihe ring and an mcrease tn the number of bromme all,ms in the aliphatlc part of the additive molecule (compounds 3-'~) increase its effect=veness In contrast, replacement or three

bromine atoms for a similar number of relatively less mobile fluorme atoms (compounds 5 and 7) appears lu somewhat reduce Ihe effectiveness of the lubricant. ThereIbre, mod=fical=on of surfaces under fr=ctmn depends not only on the persence of halogen atoms Jn the ring, but also on the number and type of h',.dogen atoms in the aSpbatic portion of the additive molecule.

18

M M {]IIIf, INI.IV el ,l/ Heal :liability

in lhu F i g u r e

ul' ih~ c~nipllund'.,

l~.~led wa,., c x a m l n e d

a n d the d u l a ai~. ~.~ve.n

"rhi:, ,.illi~ws l h u l in lhllse c':i,,¢,.., w h e n h a l o g e n alorli~, ( ~ ' u m p l l u n d

arc" ab,~enl From Iht' additive' niol¢c'ul¢, dec'~tnlp~,,ili~il

I~

,,lurl;, ,'.it h.it~ Ic'inpcralurv,,

;ind Full W¢llTlil hi,,?, I,, id~selved ~'~.~r ;i u'llllip~Jltlll~u'lv Ildrro~,~ r;lllT~' ol k'lnp~ralilr{.' 'T'h¢, rlre~it'llt.'l- ilf I-i:litll:~t'll ,'Jlllllll., iii II1~' rill{.', tllld III Ih~' d l l p h l l l l c I~U~l {,I lilt' ilddlli~.l' ITlt.ilft'ult ~ IIIt'l'tNJ'~t"., I1-i¢ It>liillt~rLIIIIll ' ,~1 iiiitltll I~r~akuh~wn a,, ~c, II a~, lti~> l c m p c ' r ; l l l , l l ' rtllllTt' il%l.'r 5~llic'll t'illl b l l ' l l k d l ~ l l

i~l.'l ii1,, (_'l_llnptlrl,,tlll ill Ihc' dLII;i lii l J b l ¢

/ ~llli

Ih~ll iii lilt' PtQi.llt' ,,llll~,, Ili,~l Lidt/lllVc'l, ~ i l t i ~i { ~llllpal:ill~,t'lV hll.~ll l i i l l l : i l hrl.>,'idklllt ii h.~.llil~t, rUlllrt - (al~pi

I,Jfl

If~tl l_ I ,it,' Ili¢ IIIir.,I t'llc'lltvc' :llld llll'V l t l l k

i'ullv liver ;I I ; l i i l v hl.,,..,h h'llll~i'l:iill,t'

i;lilQi~ ( a p p i

I'~(t

llr¢ilk dll~,rl

,4till ( )

SUMMARV

I

Fhllylialog~'n i.'(.lll[iilnllll.' c ycli~ c'~ttq,, ~1 tl:|h){,en ~lc'elic' Jc'ld~., were e l l a l l l l r l e d

a,, l u l ' i r i c a l i n g uil addillV~,i. W i l h c tililrint' ;]hliil,, ill lh¢ l l n ~ LII,, Ih~, nulnb~'r ol I-ifll mint" :lioni,, in Ih¢ allph.'illc

p a r l ~ll' Iht' illlll¢c'ul¢ inc'f¢iis¢~, l l w ~fl'cci ~tl the adch

Iivt' ;11btl illC'retl:.~t',.., Rfpli.lt'¢nit~lll i~l I"lll.lnllnt' iJltlrlP., flit i-]ul_lrlrlt' til(~in,, in lh¢ alir~fi:l lie p a r l ill' 1ti¢ rli,llc'c'ull( I~i~c'r', lhe ¢flel'l (,i Ili~ a d d i l l V l > c o n , ~ i d c r a h k Ttit" lii{.,h~'r Ilia' i n l l l a l It'llll_iertllUl't > ltl dc, i.'lilllpl~,,lll~in ;llld Ih¢ it_iw~r lilt' i;Ih~ Ill ;IddlllV~' I l r C a k d l i w n , Ihe lillff¢ t'pit'c'll'¢t ~ III1.' ,.lddlllvl.' REFERENCES

I. A. M. KI.JLI'I'EV, Khlrlil~,i i Iq'l~lirllih.tl_41~.;i |~ll,.,,idltk k rll;J,.,l:lrli i ll.lphv.'lrtl, p llllt, KhilTiisa, MiI;ictlw, ll172 2 V. F. P E R V E Y E V , Yu. T. G O R D A S H , K P. M U I t Y G I N A ,,nd I. I. S R E B D O L ' S I I A Y A , N~'llc~khlniiya 14, t, 4'70, ll17,4 3 M, M, GLISEINI.IV, T, G, KYAZ, I M O V A , R. S. BABAYEV arid M, I], M].RZOYEVA, NCrhJ..,y,.,h~.'hcrlrlVw' t'hr'~' hrqiF111.11s,.ll,,nlll1~l,,h~l~ ~, dlurllIViilrl,.,irll¢l¢, U~.'h zlJp A/t'l'h llrl l,J, ~-I.

X,4, li~TS ,4 lVl. M. G U S E I N O V , T. G. K~ A Z I M O V A , R. S. B A B ~ E V ,~nd I. M. A K H M E D O V , ZhNin or!.,,ari I~liilrlil 13, %, ~#%') I ~i,